US4416940A - Simulated weathered-copper coatings for metal - Google Patents
Simulated weathered-copper coatings for metal Download PDFInfo
- Publication number
- US4416940A US4416940A US06/325,653 US32565381A US4416940A US 4416940 A US4416940 A US 4416940A US 32565381 A US32565381 A US 32565381A US 4416940 A US4416940 A US 4416940A
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- US
- United States
- Prior art keywords
- copper
- color
- patina
- process according
- base coat
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- Expired - Fee Related
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Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B44—DECORATIVE ARTS
- B44F—SPECIAL DESIGNS OR PICTURES
- B44F9/00—Designs imitating natural patterns
- B44F9/10—Designs imitating natural patterns of metallic or oxidised metallic surfaces
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
- B05D5/06—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain multicolour or other optical effects
- B05D5/067—Metallic effect
- B05D5/068—Metallic effect achieved by multilayers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S428/00—Stock material or miscellaneous articles
- Y10S428/913—Material designed to be responsive to temperature, light, moisture
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
- Y10T428/251—Mica
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
- Y10T428/256—Heavy metal or aluminum or compound thereof
Definitions
- the present invention relates to a process for application of coatings to a substrate to impart a simulated weathered-copper appearance and articles produced thereby.
- the process may utilize water-reducible and solvent-based "visulescent" (defined below) coatings which result in the perception of color effects dependent on viewing angle or the angle of incident light.
- copper metal usually in the form of sheet copper
- Both historical landmarks and modern architecture utilize copper panels because of its favorable weight, strength, formability and aesthetic appeal.
- External copper as a building component is widely used for external purposes in siding, roofing and structural components. More recently, additional applications have been found to supply imaginative, decorative applications for internal purposes. Architects are constantly developing new techniques for using copper, including the concept of laminating copper to other materials, such as plywood and asbestos.
- Copper sheet and metal applications are unique in that the fresh metallic copper appearance changes on aging and exposure. Weathered-copper proceeds through multiple changes each affording a different color perception. These various colors of copper enhance the structures on which it is used and provides a distinctive character thereto. Copper, when exposed to the elements, passes through various brown and green shades and ultimately weathers to a blue-green or gray-green color, a process which takes five to fourteen years. The brown shades are called “statuary finishes” and the green shades are called “patinas.” Statuary finishes (metal to brown) can be maintained somewhat by application of raw linseed oil. Patina finishes depend on the weathering property of copper and occur over many years of aging.
- the instant process relates to a process for imparting the desirable weathered-copper appearance to various substrates which overcomes the undesirable aspects of metallic copper.
- Such coated substrate can readily be used in place of the metal sheeting and yet provide the aesthetic copper metal and patina appearances which are immediate, relatively permanent and are not dependent on weathering.
- a further object is to provide a process for coating a substrate, especially metal substrate, whereby a finish is applied to the substrate thereby imparting a weathered-copper appearance to the substrate.
- a further object relates to a two-step process for imparting a simulated weathered-copper appearance to a substrate which comprises first applying an opaque pigmented base coat containing a dominant patina-color-producing colorant to a primed or unprimed substrate; curing said base coat; applying a second non-opaque top coat containing one or more copper-color-producing additives in an amount sufficient to impart a simulated weathered-copper appearance having both a copper metallic appearance by reflection of incident light from the top coat and a patina appearance by transmission of light to and reflection from the base coat with perception of the various color effects being dependent on the viewing angle or the angle of incident light.
- Another object relates to the coating of a metal substrate, especially a coil coating stock according to the above-described process wherein said base coat comprises at least one film-forming binder, an organic carrier for said binder, an opacifying agent, pigment and other additives sufficient to impart desirable coating characteristics including hiding power, weatherability, opaqueness, and patina color; and wherein said top coat comprises at least one film-forming binder, an organic carrier for said binder and at least one copper-color-producing additive.
- a yet further object relates to articles coated with the instant compositions according to said process including metal objects such as coil coatings and metal roof and siding panels whereby said articles will have the aesthetic weathered-copper appearance, be useful as a building and/or decorative material in place of copper metal and copper sheeting, but advantageously not be subject to continued weathering and thus having a permanence with regard to surface characteristics and color.
- FIG. 1 shows workable and preferred ranges for the top coat parameters in the process of the invention.
- the coatings which provide a decorative copper-like weathered appearance, are applied to substrates via conventional coating techniques, as for example, spray, brush coat, flow coat, dip coat, roll coat, etc.
- the substrates can be a primed or non-primed wood, metal, glass, plastic, fiber reinforced plastic such as styrene, copolymers of styrene, polypropylene, and the like.
- These coatings are especially suited for exterior finishes for metals such as coil coating, siding, and roofing shingles.
- the substrate may be cured by conventional techniques to produce a film thereon having excellent characteristics including flexibility and adhesion with good resistance to humidity, salt spray, light, chalking, and organic solvent.
- the coating is advantageously applied to siding, steel panels or venetian blind stock in a continuous process. After each application, the coated panel is subjected to a rapid cure schedule for about 20 to 40 seconds to achieve a peak metal temperature cure of about 400°-500° F., followed by rapid water-quench cooling.
- An alternative cure method involves heating the coated stock at 375° F. for twenty minutes followed by cooling by water spray or water quench.
- the instant invention for imparting a weathered-copper appearance to a substrate, and preferably a metal such as coil coating stock for roofing and siding applications depends on the unique multicoating process whereby a substrate, preferably primed in advance, is first treated with a specific base coat.
- the base coat which contains usual ingredients in such coatings must result in an opaque coating and must have the necessary dominant colorants to provide the dominant patina color which will be observed in the final object by transmission.
- the base coat will be formed from suitable film-forming binders which provide the necessary properties to the coating on application such as flow and on curing the permanence to afford considerable resistance against weathering and oxidative and light stability.
- the dominant pigment and vehicle, binder and paint additives must be compatible one with another as well as being compatible with the diverse second coat to be applied over the cured first coat.
- the base coat be essentially opaque and non-transparent so that the dominant patina can be projected as a transmitted color.
- the top coat be non-opaque and substantially transparent to allow perception of the dominant patina color of the base coat.
- pigments having the dominant colors green, blue, gray, and mixtures are useful. It is recognized that a true patina color can be any of a number of intermediate shades ranging from green to blue. A prominent blue patina may provide a more aesthetic appearance for roofing panels usually observed from a distance whereas a more prominent green or gray-green patina will be more desirable for decorative purposes and panels and objects to be visually observed at close range.
- Suitable base coatings in accordance with this invention require an extremely finely divided patina-color-producing pigment or colorant having an average particle size of 10 microns or less.
- the primary colorant usually comprises from about 4 to about 30 weight percent of the coating, the remainder being binder, usually paint additives, carrier solvent, processing and leveling agents, fillers, and opacifying pigments.
- film-forning binders selected include one or more or the commercially available thermoset resins used in conjunction with one or more typical vehicles, the binder and vehicle being selected in type and properties dependent on whether the vehicle is an organic type vehicle or whether the coatings are aqueous based coatings either latex type or water dispersible.
- Suitable binders can be formulated from commercially available resins such as vinyls, halogenated vinyls, polyhalogenated vinyls, styrenes, acrylics, polyesters, urethanes, and mixtures thereof.
- Especially preferred binders for solvent base systems are polyvinylidene fluoride resins because of their excellent durability and weathering characteristics.
- a combination of resins will be selected to provide an optimum mixture providing both weathering and film-forming characteristics.
- Such combination of binders are well known in the art.
- An especially preferred combination includes mixtures of polyvinylidenefluoride resin and acrylate type resins.
- Mixtures of binder advantageously contain about 50 to about 80 and preferably 65-70 weight percent polyvinylidene fluoride and from about 20 to about 50 and preferably about 30 to 35 weight percent acrylic resin.
- a primer coat of a suitable primer should be applied and cured before application of the multicoat system of this invention.
- conventional primers such as DEXTER 165 (Dexter Midland Corporation), AQUALURE, PPG3305 (PPG Industries), and similar primers are satisfactory.
- Especially preferred primers used in the embodiments herein include the non-corrosive primers and preferably commercial primers known and marketed by Glidden as AQUALURE primers.
- the top coat is similarly critical to the production of the finished coating and to the simulated weathered-copper appearance, said total appearance having both a copper metallic appearance when viewed by reflected light and a patina appearance by transmitted light.
- the top coating contains a visulescent additive sufficient to insure that the coated substrate exhibits visulescence; that is, the coated object appears to exhibit different colors depending on the visual angle (plane) of observation and/or on the angle of incident light impinged thereon.
- a visulescent additive, colorant, or pigment, sometimes used interchangeably herein, is any additive that when formulated in critical amount in a multiple coating system produces a visulescent effect.
- top coats In order for the top coat to satisfy the novel function required to produce a weather-resistant simulated weathered-copper-colored coating, there are two parameters that are interrelated and that must be critically controlled.
- a visulescent additive preferably a solid matter with suitable properties capable of reflecting visible light and also capable of transmitting visible light.
- Such additive must be a copper-color-producing additive so that the coating will produce a copper coloration by reflection and yet allow light to pass through and be transmitted to the dominant undercoat so that it can be reflected therefrom to produce the diverse patina color.
- the top coat may be formulated from the same resin binder as used in the base coat or may utilize a different binder system compatible therewith.
- the top coat will contain mixtures of the film-forming resins. It is preferred to use the same resin system in the top coat, but such total system must differ from the base coat in various aspects.
- the top coat cannot be opaque and hence must not contain fillers, pigments or other additives that would make the top coat opaque. Impinged light must be able to transverse the top coat and thus allow the multiple color effect of the instant invention.
- the two related parameters to satisfy the top coat requirement and provide the visulescent coating are the film thickness and the concentration of the copper-color-producing additive. Many combinations of these parameters will allow for the novel coatings of the instant invention. Although the inventors do not desire to be bound thereby, the FIG. 1 graphically depicts workable and preferred ranges for these parameters. Referring to FIG. 1, it is seen that the desirable properties are expected when the top coat film thickness is varied from about 0.1 mil to about 1.0 mil and preferably in the range of about 0.3 to 0.6 mil and when the copper-color-producing additive concentration is varied between about 0.50 and about 6.0 weight percent, basis total weight of top coat, preferably 0.75 to about 3.5 weight percent. These parameters will obviously change to some degree with the choice of copper-producing additive.
- the visulescent effect When the pigment concentration is increased beyond the maximum, the visulescent effect will be replaced by a type of opulescence or pearl effect. In this condition, the color produced in the top coat by reflection is dominant over the color resulting from the base color by transmission. Thus when a thinner coating is applied, the additive concentration may be increased and visa versa when the additive concentration is low, a heavier top coat may be applied.
- the additives which can provide the visulescent characteristics and the copper-color required in the instant invention include a large number of products known to the coating art and include pigments known in the trade as iridescent pigments.
- Such additives include finely divided elemental metal materials including copper and bronze preferably in the form of a powder, but sometimes in other forms such as for example prisms, plates, pellets and even combinations thereof.
- Such pigments are oft-times treated with a chemical treating agent such as for example a metal salt of a long chain saturated or unsaturated, organic acid, i.e., sodium stearate, which can render them more suitable for the instant purposes.
- a chemical treating agent such as for example a metal salt of a long chain saturated or unsaturated, organic acid, i.e., sodium stearate, which can render them more suitable for the instant purposes.
- other useful materials that exhibit some or all of the desirable properties required for the instant invention include variously treated micas.
- MEARLIN® The Mearl Corporation
- Luster Pigments especially the copper and bronze variants which can be used separately or in combination.
- These pigments are said to differ from conventional pearlescent pigments in that they have been given a special chemical treatment (see U.S. Pat. No. 4,134,776).
- the invention is not limited to copper-containing pigments.
- a number of useful copper-color-producing additives are exemplified in the following patents and these are specifically incorporated herein by reference. Such patents include: U.S. Pat. Nos.
- Preferred coatings are prepared from finely divided copper pigments and/or suitable mica additives treated with a titanium dioxide and/or an iron oxide. Bronze powders containing sufficient copper and zinc metals will also produce a wide range of copper-like colorations ranging from gold to copper colors.
- the coatings produced in the instant invention are not dependent on after-treatment of the coated substrate following cure.
- the instant coatings when applied to metal stock provide a relatively permanent color and coating which is not subject to the weathering variables of the copper metal and copper sheets. Panels colors having a wide range of copper colors can be produced; non-weathered effects, intermediate weathered effects, and advanced weathered effects can be made to specification.
- the best mode water-based coatings can be prepared from non-copper-containing treated mica such as commercially available MEARLIN® Antique Copper Luster Pigment used in conjunction with a commercially available acrylic latex base coat and top coat, as for example, Pigmented and Non-Pigmented AQUALURETM 1000; AQUALURE 3000 and AQUALURE 5000. It is anticipated that a wide range of acrylic latexes will be suitable in the practice of this invention.
- the additive must have an average particle size of about 30 microns or less and preferably in the range of about 10 to 30 microns.
- the additive is a metallic additive such as copper powder, it is desirable to use powder having a leaf content of at least about 50 percent leaf particles with most desired compositions having an average particle size in the range of 5 to 20 microns and a leaf content of 65 percent.
- Organic-based coatings and aqueous-based coatings can advantageously use various polymer resin systems; e.g., those made from polymers of methacrylic acid, acrylic acid, and their mixtures, copolymers and terpolymers of methacrylic acid esters with styrene and/or vinyl acetate, or copolymers and terpolymers of methacrylic acid and esters with acrylic acid and esters and/or acrylonitrile.
- polymer resin systems e.g., those made from polymers of methacrylic acid, acrylic acid, and their mixtures, copolymers and terpolymers of methacrylic acid esters with styrene and/or vinyl acetate, or copolymers and terpolymers of methacrylic acid and esters with acrylic acid and esters and/or acrylonitrile.
- polyvinyl chloride particularly those plasticized with conventional plasticizers such as 2-ethyl hexanol or 2-ethoxyethanol-1 and latices of copolymers of vinyl and vinylidene chloride and vinylidene fluoride.
- Aqueous emulsions of alkyd resins and modified alkyds are also useful.
- Suitable binders include acrylate polymers and acrylic type polymers formed from other vinyl compounds including vinyl chloride and acetate; especially preferred are polymerized esters of acrylic acid or its homologs, e.g. methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, octyl methacrylate, polymerized styrene, polyhydric alcohol-polybasic acid resins. Interpolymers of two or more of such compounds and mixtures of such resins can also be used as suitable binders.
- advantageous binder systems include polyesters, silicon polyesters, vinyls, urethanes and the like.
- Preferred system incorporated polyvinylidene halides especially polyvinylidene fluoride and most preferred systems because of their enhanced durability to external conditions and climates are the multiple binder systems which have a major portion of polyvinylidene fluoride used in conjunction with a lesser portion of a different thermoset binder, such as, for example, acrylic binders.
- Suitable emulsion systems include those of vinyl resins by which we mean to include vinyl acetate, vinyl chloride, vinylidene chloride, and the like; those of hydrocarbon polymers and copolymers, polyethylene, polypropylene and oxygenated or halogenated derivatives of same by which we mean to include polybutadiene, oxygenated polybutadiene polyisoprene, oxygenated polyisoprene, butadiene-styrene, butadiene-vinyl toluene, isoprenestyrene and the like; acrylic latices by which we mean to include polymers and copolymers containing units of acrylic acid, methacrylic acid, their esters, and acrylonitrile; alkyds; reaction products of vinylic hydrocarbon monomers with unsaturated materials such as the reaction product of maleic acid with styrene.
- aqueous systems are those formulated from water-reducible acrylic thermoset coatings used in conjunction with non-copper-containing treated mica pigments.
- composition of this invention may contain any number of other additives usually used in such coatings including coloring pigments, extender pigments, driers, bodying agents, stabilizers, defoamers, preservatives and the like.
- Additional additives serving to promote suitable dispersion of the metal powders in conjunction with the other agents described above can be any of the common surfactants and/or wetting agents used in paint formulation.
- the coating may be applied to the substrate in the usual manner including reverse rollcoating; spray; direct rollcoat; electrostatic and handbrushed methods.
- the coating is applied to residential siding, steel panels or venetian blind stock.
- the coated panel is subjected to a rapid cure schedule for 30-40 seconds at 470° F. (peak metal temperature), followed by rapid cooling in a water quench.
- An alternate cure method involves heating at 375° F. for twenty minutes followed by water quench or water spray.
- Flexibility is determined by observing cracking and tear-off observed on a single band of the panel. Cracking is rated 0-10; values of 9 or above very acceptable. Tear-off (complete removal of coating using clear cellophane tape) is rated 0 (no removal) to 100 (100% tape off).
- Pencil Hardness After a specimen has been conditioned for twenty-four hours in a thermo-hydrostated chamber at a temperature of 20° ⁇ 1° C. and a relative humidity of 75 ⁇ 3%, it is set horizontally in the chamber and scratched with a sharpened pencil. Th value is expressed by the hardness of the hardest pencil which cannot make a scratch on the coated surface. B hardness values are satisfactory with progressive values B ⁇ HB ⁇ F ⁇ 1H ⁇ 2H ⁇ 3H are most desirable. F values of pencil hardness are very satisfactory.
- Carbon Arc Weatherometer An accelerated weathering test consists of subjecting the coated panels to a water spray in a weatherometer whereby the panels while being rotated are subjected to definite intermittent cycles of water spray and light (ultraviolet). An acceptable coating will withstand over 1,000 hours of weathering and superior coating will show very little deterioration at 2,500 hours.
- MEK Resistance Test A cloth soaked with methyl ethyl ketone is stroked upon the coating surface using finger pressure. The number of strokes to failure of the coating is observed and recorded. Values of 50 rubs or better are acceptable values.
- a galvanized steel panel was first treated with a 0.30 mil coating of AQUALURE Primer 631-L-128 (Glidden Coatings & Resins). Following cure an opaque green base coat of VISULURETM No. 307-Green (Glidden) was applied using a #38 draw down wire, was oven cured at 470° F. and water quenched to yield an opaque patina colored coating of 0.80 mil thickness. Thereafter, a non-opaque top coating VISULURETM M-301 (prepared from the same binder as base coat but having no opacifying pigment) containing 3.5 percent by weight MEARL® (Mearl Corporation) Antique Copper Pigment Luster Pigment is deposited using a draw down wire, oven cured at 470° F.
- the resulting panel exhibited a simulated weathered-copper appearance estimated to be equivalent to that of a 10-year weathered copper sheet and as an overtone exhibited a copper metallic appearance in reflected light.
- the coated panels were analyzed using a Match-Scan (Diano Corporation) Scanning Spectrophotometer having polychromatic illumination from a tungsten source lamp diffused by an integrating sphere with 6.5-degree viewing.
- Match-Scan Diiano Corporation Scanning Spectrophotometer having polychromatic illumination from a tungsten source lamp diffused by an integrating sphere with 6.5-degree viewing.
- the standard Flexibility Test gave a 2T rating with no cracking, no tape off and exhibited a F pencil hardness (Eagle Turquoise).
- the resin binder system in the top coat and base coat is a mixture of 70 percent polyvinylidene fluoride and 30 percent acrylic resin. It is noted that the Mearl Pigment used in this Example contains no metallic copper.
- the instant process can be used as a water-reducible coating to coil coating stock.
- a 24-gauge galvanized steel panel is first treated with an 0.25 to 0.35 mil coating of AQUALURETM (Glidden) 128 corrosion resistant primer.
- an acrylic latex opaque base coat of AQUALURE 3000 (Glidden) pigmented with a blue-green inert colorant is applied by draw down #26 followed by oven curing at 435° F. peak metal temperature and water quenched to give an opaque patina-like coating of about 0.9 mil thickness.
- a non-opaque top coat consisting of unpigmented AQUALURE 3000 containing 3.5 percent by weight MEARL® Antique Copper Luster Pigment (Mearl Corporation) is deposited using a #12 draw down wire, oven cured at 435° F.
- the resulting panel will give a simulated weathered copper patina color estimated to be equivalent to a copper sheet weathered 6 to 8 years and as an overtone will exhibit a copper metallic appearance in reflected light.
- Example 1 When the procedure of Example 1 is repeated but the polyvinylidene/acrylic binder system is replaced by an equivalent weight amount of a silicone polyester resin binder, the coated panel will exhibit a simulated weathered copper appearance similar to that produced in Example 1. This product will be especially suitable for external building uses.
- Example 1 When the procedure of Example 1 is repeated using a urethane formulated binder, a satisfactory coating having a weathered-copper appearance will be obtained.
- Example 1 When the procedure of Example 1 is repeated using a finely divided copper metallic pigment, OBRON SF-50 UP (trademark of Obron Corporation, 98.5% through 200 screen) having a leafing value of greater than 50 percent, in place of the non-copper-containing additive, a coated panel exhibiting a weathered-copper appearance similar to that obtained in Example 1 will be produced.
- OBRON SF-50 UP trademark of Obron Corporation, 98.5% through 200 screen
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- Paints Or Removers (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
Abstract
Description
______________________________________ DIFFUSED PERCENT REFLECTANCE WAVE BASE COAT LENGTH IN BASE AND HEAVY NANOMETERS COAT TOP COAT TOP COAT ______________________________________ 400 20.45 15.55 12.50 420 24.75 18.26 14.34 440 26.93 19.62 15.14 460 30.19 21.60 16.33 480 33.03 23.23 17.45 500 35.26 24.62 18.45 520 37.09 25.93 19.51 540 37.64 26.69 20.39 560 35.08 26.28 21.03 580 31.12 25.43 21.69 600 29.28 25.34 22.48 620 26.90 24.31 22.13 640 26.41 24.40 22.41 660 26.03 24.45 22.65 680 25.14 24.05 22.59 700 25.98 24.97 23.51 Tristumulus X 28.71 23.31 19.76 Tristumulus Y 33.57 25.57 20.71 Tristumulus Z 32.19 23.11 17.62 YI Index 18.781 23.448 27.935 L* 6.08 7.93 9.60 ______________________________________ *Visually it was observed that the Visulescent effect of the weathered coppercolored panel would essentially disappear on the application of a much heavier top coat (Column 3 above).
Claims (13)
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US06/325,653 US4416940A (en) | 1981-11-30 | 1981-11-30 | Simulated weathered-copper coatings for metal |
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US06/325,653 US4416940A (en) | 1981-11-30 | 1981-11-30 | Simulated weathered-copper coatings for metal |
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Cited By (30)
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US4484400A (en) * | 1982-04-19 | 1984-11-27 | The Ironees Company | Copper-metallized fabric for an ironing board cover |
US4546007A (en) * | 1983-05-21 | 1985-10-08 | Yoshiaki Abe | Multi-layer coating method based on spectral reflectance of white or gray colors |
US4552780A (en) * | 1983-09-27 | 1985-11-12 | Yoshiaki Abe | Multi-layer coating method based on differential spectral reflectance |
US4605687A (en) * | 1983-08-26 | 1986-08-12 | Inmont Corporation | Multilayer automotive paint system |
US4877077A (en) * | 1988-05-13 | 1989-10-31 | Home Fashions, Inc. | Vertical coextruded pearlescent louver for vertical blinds |
US4950507A (en) * | 1987-12-07 | 1990-08-21 | Toyota Jidosha Kabushiki | Method for applying a coating composition having a sparkling luster containing FeO3 particles of hexagonal plate-like shape |
US5075137A (en) * | 1989-10-20 | 1991-12-24 | Kuras Leonard C | Method of weathering models |
US5119871A (en) * | 1990-04-06 | 1992-06-09 | The B. F. Goodrich Company | Opacified pearlescent multilayer louver for vertical blinds |
US5160381A (en) * | 1991-06-26 | 1992-11-03 | Fumigation Maritime Ltee | Method for forming artificially and rapidly patina on copper, products thereof and solutions therefor |
US5338566A (en) * | 1990-01-05 | 1994-08-16 | Avco Corporation | Method utilizing a ceramic for temperature measurement |
US5410212A (en) * | 1993-04-01 | 1995-04-25 | General Electric Company | Soft white reflector lamp |
US5496630A (en) * | 1993-09-13 | 1996-03-05 | The Geon Company | Thermoplastic multilayer louver with a polished metal look |
US5871827A (en) * | 1996-06-21 | 1999-02-16 | Ciba Specialty Chemicals Corporation | Finishes containing light interference pigments |
AU725889B2 (en) * | 1996-06-21 | 2000-10-26 | Ciba Specialty Chemicals Holding Inc. | Finishes containing light interference pigments |
US6485781B2 (en) * | 1999-05-26 | 2002-11-26 | Basf Corporation | Metal roofing shingle stock and method for making it |
US20040116554A1 (en) * | 2001-11-29 | 2004-06-17 | Nirupama Karunaratne | White pearlescent paint compositions and coatings |
US20050011750A1 (en) * | 2003-07-17 | 2005-01-20 | Crown-Pn L.L.C. | Simulated patina for copper |
US20050153093A1 (en) * | 2004-01-09 | 2005-07-14 | Sung Chang | Prefab-type waterproofing structure and method for fabricating the waterproofing structure |
US20050235599A1 (en) * | 2004-03-23 | 2005-10-27 | Kalkanoglu Husnu M | Shingle with sharply defined tabs separated by slots and method of making |
US20060019108A1 (en) * | 2004-07-24 | 2006-01-26 | Stefan Hoveling | Method for producing an inorganic cover layer on the surface of a product and panel-shaped or strip-shaped product |
US7018677B2 (en) | 2003-07-17 | 2006-03-28 | Crown-Pn L.L.C. | Simulated patina for copper |
US20080060552A1 (en) * | 2006-09-07 | 2008-03-13 | Yang Yong | Color Foundation Coat and Color Top Coat Paint System |
US20110183112A1 (en) * | 2010-10-06 | 2011-07-28 | Kirk Matthew Bailey | Roofing material with directionally dependent properties |
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US20140109495A1 (en) * | 2008-03-06 | 2014-04-24 | Stuart Charles Segall | Relocatable habitat unit having radio frequency interactive walls |
US9815318B1 (en) | 2014-03-10 | 2017-11-14 | Joseph Steimann | Method of creating weathering effects on models |
US10946611B2 (en) * | 2017-01-26 | 2021-03-16 | Composecure, Llc | Patinated or patina-ready metal transaction cards and manufacturing process |
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US4484400A (en) * | 1982-04-19 | 1984-11-27 | The Ironees Company | Copper-metallized fabric for an ironing board cover |
US4546007A (en) * | 1983-05-21 | 1985-10-08 | Yoshiaki Abe | Multi-layer coating method based on spectral reflectance of white or gray colors |
US4605687A (en) * | 1983-08-26 | 1986-08-12 | Inmont Corporation | Multilayer automotive paint system |
US4552780A (en) * | 1983-09-27 | 1985-11-12 | Yoshiaki Abe | Multi-layer coating method based on differential spectral reflectance |
US4950507A (en) * | 1987-12-07 | 1990-08-21 | Toyota Jidosha Kabushiki | Method for applying a coating composition having a sparkling luster containing FeO3 particles of hexagonal plate-like shape |
US4877077A (en) * | 1988-05-13 | 1989-10-31 | Home Fashions, Inc. | Vertical coextruded pearlescent louver for vertical blinds |
US5075137A (en) * | 1989-10-20 | 1991-12-24 | Kuras Leonard C | Method of weathering models |
US5338566A (en) * | 1990-01-05 | 1994-08-16 | Avco Corporation | Method utilizing a ceramic for temperature measurement |
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US20090297792A1 (en) * | 2003-07-17 | 2009-12-03 | Percy Greenberg | Simulated patina for copper |
US7267735B2 (en) * | 2004-01-09 | 2007-09-11 | Sung Joo Chang | Prefab-type waterproofing structure and method for fabricating the waterproofing structure |
US20050153093A1 (en) * | 2004-01-09 | 2005-07-14 | Sung Chang | Prefab-type waterproofing structure and method for fabricating the waterproofing structure |
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